JPS6044557A - Insoluble monoazo compound and dyeing using it - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [when X is methoxycarbonyl, Y is methoxycarbonyl, or ethoxycarbonyl, when X is phenylsulfonyl, methylsulfonyl, etc., Y is H, methoxycarbonyl, or ethoxycarbonyl; R is H, methyl, or ethyl; K is group shown by the formula II-formula V (R1 is H, chloro, methyl, acetylamino, etc.; R2 is H, chloro, methoxy, etc.; R3 and R4 are H, 1-4C alkyl, aryl, etc., and R3 and R4 are not H at the same time; R5 is chloro, or methyl; R6 is H, methyl, or phenyl; R3 is H, 1-4C alkyl, etc.)]. EXAMPLE:A compound shown by the formula VI. USE:Dye for dyeing hydrophobic fiber, especially polyester, triacetate fiber in clear purple, red, yellow, etc. with improved fastness to light, heat, and wetting. Low white polluting properties. PREPARATION:An aniline derivative shown by the formula VII is diazotized, and coupled with a coupling agent shown by the formula KH.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a monoazo compound and a method for dyeing hydrophobic fibers using the same. More specifically, when the formula (11) is a methoxycarbonyl group or an ethoxycarbonyl group, Y is a methoxycarbonyl group or an ethoxycarbonyl group, and when X is a phenylsulfonyl group, a methylsulfonyl group, or an ethylsulfonyl group, Y represents hydrogen, methoxycarbonyl group, or ethoxycarbonyl group (4 each) It8 (however, in formulas (II), (III), (IV), and M, R1 is hydrogen, chloro, methyl group, methoxy group, ethoxy group, acetyl group) Amino group, propionylamino group, benzoylamino group, methylsulfonylamino group,
or ethylsulfonylamino group, R2 is hydrogen, chloro, methyl group, methoxy group or ethoxy group, R3, 几4
is hydrogen, an alkyl group having 1 to 4 carbon atoms, an allyl group, a benzyl group, a cyanoethyl group, an alkoxyalkyl group having 3 to 4 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an acyloxyalkyl group having 4 to 6 carbon atoms , an alkoxycarbonylalkyl group having 3 to 7 carbon atoms or an alkoxycarbonyloxyalkyl group having 4 to 7 carbon atoms (however, R3 and R4 are not both hydrogen); R is a chloro or methyl group; R6 is an alkoxycarbonyloxyalkyl group having 3 to 7 carbon atoms; Hydrogen, methyl group or phenyl group, R7p
R8 represents an alkoxycarbonyl group having 2 to 5 carbon atoms.
is hydrogen 1. Alkyl group having 1 to 4 carbon atoms or 4 to 7 carbon atoms
each represents an alkoxyalkyl group. )] and a method for dyeing hydrophobic fibers using the monoazo compound.

The monoazo compound of formula fI) according to the present invention is a monoazo compound of formula (VD(
It is produced by diazotizing the aniline derivative represented by the formula (wherein X, Y, R are as defined above) and coupling it to a coupling component represented by K H (K is as defined above).

Specific examples of the aniline derivative represented by formula (Vl) used in the present invention include 2-cyano-4-methoxycarbonyl-5-hydroxy-6-medoxycarbonyl-aniline, 2-cyano-4- Ethoxycarbonyl-5
-Hydroxy-6-ethoxycarbonyl-aniline, 2
-77/-j-phenylsulfonyl-5-hydroxy-
Aniline, 2-cyano-4-ethylsulfonyl-5-hydroxy-aniline, 2-cyano-4-phenylsulfonyl-5-ethoxy-aniline, 2-cyano-4-ethylsulfonyl-5-methoxy-aniline, 2-cyano −
Examples include 4-phenylsulfonyl-5-hydroxy-6-ethoxycarbonyl-aniline, 2-cyano-4-ethylsulfonyl-5-hydroxy-6-meth)oxycarbonyl-aniline, and these are new compounds. Yes, ethoxymethylenemalondinitrile and X Cl-12
It is produced by condensing a ketone represented by COCH2Y (X, Y mean the above) in the presence of sodium alcoholade, and then reacting this condensate with an alkylating reagent such as dimethyl sulfate or diethyl sulfate, if necessary. It is something that

Coupling component formula (II) used in the present invention ~
(V) is a camping component commonly used when producing azo disperse dyes. For example, tbN-ethyl-N-
Cyanoethyl-aniline, N-methyl-N-acetoxyethyl-meta-toluidine, N,N-diethyl-2-acetyl-methamine, N,N-sialyl-2-methoxy-5-
Acetylamino-aniline, N,N-diethyl-3-ethylsulfonylamino-aniline, N,N-c(I-
hydroxyethyl)-3-benzoylamino-aniline, N,N-di(methoxycarbonylethyl)-3-
Acetylamino-aniline, N,N-c(β-methoxycarbonyloxyethyl)-3-acetylamino-aniline, ortho-cresol, 3-chloro-phenol, 1-phenyl-3-methyl-pyrazolone, ■-phenyl-3 -Methoxycarbonylupirasolone, 1-(3:
4'-dichloro-phenyl)-3-methyl-pyrazolone, nibutyl-3-cyano-4-methyl-6-hydroxypyridone (-2), 1-(γ-methoxyethyl)-
3-cyano-4-methyl-6-hydroxypyridone (
-2) etc. are exemplified.

Diazotization and camping in the present invention can be carried out by conventional methods. For example, when the aniline derivative of formula (■) is treated with nitrosyl sulfuric acid in concentrated sulfuric acid or a mixed solution of acetic acid and propionic acid at 5°C or lower, it is easily diazotized.
When the diazotized solution is added to an aqueous solution or dispersion containing the coupling component at 10°C or less, coupling and acidification is easily carried out. At this time, it is desirable to adjust the pH by adding soda ash, sodium chloride, etc. as necessary.

The monoazo compound obtained by the present invention is a hydrophobic compound (
It is particularly suitable for dyeing or printing polyester fibers, triacetate fibers, etc. In dyeing, the azo compound is dispersed with a dispersant and, if necessary, mixed with other dyeing aids to form a dye composition. That is, the monoazo compound is a formaldehyde condensate of naphthalene sulfonic acid,
In the presence of an anionic dispersant such as lignin sulfonic acid, sulfated creosote oil, or a nonionic activator such as a block copolymer of ethylene oxide and propion oxide, or an ethylene oxide additive of alkylphenol, and a small amount of water, Alternatively, the dye composition can be obtained by sufficiently wet grinding using a sand mill or the like. Using this composition, conventional high-temperature dyeing, carrier dyeing, thermosol dyeing, textile printing, etc. are carried out. In the case of continuous dyeing, it is desirable to use a migration inhibitor such as sodium alginate and a reduction inhibitor, and in the case of textile printing, it is desirable to use a natural paste, a synthetic paste, a PL-I regulator, a male dye, etc. in combination. Furthermore, by overprinting with a discharge printing paste containing a reducing agent and an alkaline agent, pattern printing such as shi, anti-discharge printing, and πf discharge printing can be performed.

The monoazo compound according to the present invention can be dyed in hues such as purple, red, and yellow, but the hue is extremely clear and has excellent light fastness, heat resistance, and moisture fastness. What can be particularly emphasized is that since the compound of the present invention has a hydroxyl group or a carboxylic acid ester group, undyed compounds can be easily removed with an alkaline agent, there is little hot water staining, and there is no problem in alkaline discharge printing. It has the characteristic that white discoloration in the discharge printing area is extremely excellent even if

The present invention will be specifically described below with reference to Examples, where "part" and "1%" refer to "part by weight" and "% by weight", respectively.

Example 1 2-cyano-4 in 50 parts of acetic acid-propionic acid (4:1)
,6-C(methoxycarbonyl)-5-hydroxy-
Add 5 parts of aniline, and add 6 parts of 44% nitrosyl sulfuric acid at 3° C. or less while stirring, and stir for 1 hour to diazotize. N,
The diazotized solution is added dropwise to 300 parts of a 2% hydrochloric acid solution containing 6.5 parts of N-di(methoxycarbonylethyl)-3-acetylamino-aniline while stirring at 10°C or lower. Add 500 parts of ice water, stir for 1 hour, and separate the precipitated compounds, wash with water and dry. Compound 93λma with the following structure
x 522 n/m (85% acetone aqueous solution) Dyeing hue of polyester fiber 2-cyano-4,6-di(methoxycarbonyl)-5-hydroxy-aniline used in the red book example is synthesized as follows.

14 parts of acetone dicarboxylic acid dimethyl ester are dissolved in 70 parts of methanol, and 15 parts of a 28% sodium methylate methanol solution is added at 10° C. or below, followed by stirring for 30 minutes.

Add 7.2 parts of ethoxymethylene malondinitrile to 20
After stirring at 2°C for 1 hour, the mixture was heated to 60-65°C and stirred for 1 hour. Cool to 10°C, separate the precipitated crystals, wash with water, and dry. 6.7 parts of 2-cya/-4,6-cy(methoxycarbonyl)-5-hydroxy-aniline are obtained.

mp290-291°C (decomposition) Example 2 2-Schiff/-4 in 30 parts of acetic acid-propionic acid (4:1)
Add 3 parts of -phenylsulfonyl-5-ethoxy-aniline, and add 3 parts of 44% nitrosyl sulfuric acid at 3° C. or below while stirring, and stir for 1 hour to diazotize. N,N-diethyl-
300 ml of 1.5% hydrochloric acid solution containing 872.1 parts of acetometa
Add the diazotized solution dropwise to the solution while stirring at 10°C or below.

Add 500 parts of ice water, stir for 1 hour, separate the precipitated compound, wash with water and dry.

4.3 parts of a monoazo compound having the following structure are obtained.

λmax 530 nm (85% acetone aqueous solution) Dyeing hue boundary of polyester fiber 2-cyano-4-phenylsulfonyl-5-ethoxy-aniline used in this example was synthesized as follows.

Sodium benzenesulfinate dihydrate 4. .

2.3 parts of chloroacetone in dimethylformamide
Stir for 2 hours at 0±2°C. Pour into 200 parts of ice water, separate the precipitate, wash with water and dry. 3.2 parts of phenylsulfonylacetone are obtained. mp56-58℃, add 6 parts of phenylsulfonylacetone to 50 parts of ethanol and add 1
Add 11.6 parts of a 28% methanol solution of sodium methylate at below 0°C. 3' Stir for 0 minutes. Add 36 parts of ethoxymethylene malondinitrile to 1 part at room temperature.
The mixture was stirred for an additional 75 parts at 5°C for 30 minutes.

Separate the reaction solution in a furnace, pour the filtrate into 500 parts of water, add concentrated hydrochloric acid to make pI-1 = 2-3, and when it precipitates, separate the nut-shaped precipitate in the furnace and wash with water. . 2-cyano4phenylsulfonyl-5-hydroxy-aniline is obtained. When recrystallized from alcohol, it shows a mp of 208-211°C.

3.6 parts of 2-'/7/-4-phenylsulfonyl-5-hydroxy-aniline was stirred in 50 parts of water and 0.8 parts of caustic soda at room temperature, and 2.5 parts of diethyl sulfate was added over about 1 hour. The mixture was added dropwise and further stirred for 12 hours.

The precipitate is separated, washed with water and dried to obtain 2-cyano-4-phenylsulfonyl-5-ethoxy-aniline.

When recrystallized from alcohol, it shows an Inp of 254-257°C.

Example 3.

2-77 parts in 40 parts of acetic acid-propionic acid (4:1)
Add 3.3 parts of /-4-phenylsulfonyl-5-hydroxy-6-nidoxycarbonyl-aniline, and while stirring,
At 3° C. or lower, 3 parts of 44% nitrosyl sulfuric acid is added and stirred for 1 hour to diazotize. 1. containing 3 parts of N,N-diallyl-2-methoxy-5-acetylamino-aniline.
The diazotized solution is added dropwise to 300 parts of a 5% hydrochloric acid solution while stirring at a temperature of 10° C. or lower. Add 500 parts of ice water and stir for 1 hour. The precipitated compound is filtered out, washed with water and dried. 4.3 parts of a compound having the following structure are obtained.

λmax'5 70 nm (85% acetone aqueous solution) Dyeing color of polyester fiber Kashiwaha 2-cyano-4-phenylsulfonyl-5-hydroxy-6-nidoxycarbonyl-aniline used in this example was synthesized as follows. do.

4 parts of sodium benzenesulfinate dihydrate and 3.5 parts of ethyl γ-chloroacetoacetate are stirred in 25 parts of dimethylformamide at 90±2°C for 2 hours. It is poured into 200 parts of ice water, and the precipitated oily substance is separated by decantation and washed with a small amount of water. This crude r-phenylsulfonylacetoacetic ester was dissolved in 30 parts of ethanol, and 5 parts of a 28% methanol solution of tutholium methylate was added at 10°C or lower, followed by stirring for 30 minutes. Furthermore, 1.6 parts of ethoxymethylenemalondinitrile was added and stirred at room temperature for 30 minutes.
Stir for 30 minutes at 5±2°C. Cool and precipitate crystals are separated by furnace. 2-cyano-4-phenylsulfonyl-5-hydroxy-6-nidoxycarbonyl-aniline is obtained which exhibits an alcohol mp 2 3 1 - 2 3 3°C.

Example 4.

Acetic acid-propionic acid (4:1) 30-tone 2-cyano-
4-methylsulfonyl-5-hydroxyloxyaniline 2
．． Add 2 parts and add 3.0 parts of 44% =) rosyl sulfuric acid under stirring at below 3°C. Stir at θ±3°C for 1 hour to diazotize. The diazotized solution was added dropwise to a 2% hydrochloric acid solution containing 2.1 parts of N,N-diethylacetomethamine under stirring at 10'''C or less. 500 parts of FK water was added and the mixture was heated at 10°C.
After stirring for 1 hour, the precipitate is filtered out, washed with water, and dried. 3.4 parts of a monoazo compound having the following structure are obtained.

λmax 498 nm (85% acetone aqueous solution) Dyeing hue of polyester fiber Red 2-cyano-4-methylsulfonyl-5-hydroxy-aniline used in this example, benzenesulfinate sodium dihydrate described in Example 2 It is synthesized in substantially the same manner as 2-cyano-4-phenylsulfonyl-5-ethoxyaniline using methanesulfinic acid sodium salt instead.

Example 5 2-cyano-4 in 30 parts of acetic acid-propionic acid (4:1)
, 2.7 parts of 6-jethoxycarbonyl-4-hydroxy-aniline are added thereto, and 3 parts of the same 44% nitrosyl sulfuric acid are added at below 3°C while stirring. Diazotize by stirring for hours at total temperature.

2.3 parts of doo-butyl-3-cyano-4-methyl-6-hydroxy-pyridone (-2) was stirred in 300 parts of water with 0.2 parts of caustic soda and 7 parts of soda ash, and the Drop the diazotization solution. At this time, 20% soda ash aqueous solution is added at appropriate times, and pl-1 is adjusted to 9 to 6. The precipitated crystals are separated, washed with water and dried to obtain 4.0 parts of a monoazo compound having the following structure.

λmax 421 nm (85% acetone aqueous solution) Dyeing hue of polyester fiber Yellow Examples 6 to 46゜ In the same manner as Examples 1 to 5, the aniline derivative of formula (Vl) was diazotized and coupled to the coupling component of K H Then, a monoazo compound of formula (IJ) was obtained and Example 47
゜30 parts of the monoazo compound obtained in Example 1, Demol N
Add a small amount of water to 40 parts of Anion Dispersant 4 (manufactured by Kao Atlas) and 30 parts of Demol C (Anion Dispersant, Kako Atlas M) to form a slurry, thoroughly wet-pulverize with a sand mill to make a finely dispersed state. Dry with a tin 1/- dryer. A dye composition is obtained which is well dispersed in water. 3000 parts of water were added to 4 parts of the dye composition thus obtained to form a dispersion, and some amount of acetic acid was added to give pI-1 = 5.
The dyed fabric is then thoroughly soaped and dried to give a bright red dyeing. Good sunlight, sublimation and wet fastness properties.

Example 48 Add 1000 parts of water to 20 parts of the dye composition described in Example 4.1 to make a dispersion. A polyester processed yarn fabric is immersed, then squeezed at a 70% weight increase of 1, and once dried at 100°C. Dry heat treatment at 210°C for 60 seconds.

Further, perform reduction washing and wash thoroughly with water. A uniformly red dyed cloth is obtained.

Example 49゜Dye composition from the monoazo compound described in Example 2 4
Parts Paste 7 60 parts Tartaric acid 0.2 parts Chloric acid Cedar 0.5 parts Water 35.5 parts Total 100 parts *Material paste A mixture of the above composition is mixed in a homomixer to prepare a printing paste. This printing paste is used to stamp the polyester fiber fabric,
80 parts were dried for 30 minutes at 5°C.

Next, steaming is performed at 130° for 30 minutes to develop color. Washing with water, followed by hot water to desize, and reduction washing yields a robust red print.

Example 50゜Stannous chloride 10 parts Sanzul) 7000 (aromatic carrier) 10 parts Locust bean gum Natural rubber 12% aqueous solution 60 parts Water
20 parts total 100 parts The above was mixed in a homomixer to prepare a discharge printing paste. Example 47
Print on the red dyed cloth as described. After intermediate drying 130°20
Steam for a minute.

Then, by washing with water, hot water, and reduction washing, a dyed cloth with a vase color pattern with excellent white discoloration of the discharge-printed paste stamped area can be obtained.

Example 51゜ Carbonated soda, sound.

Glycerin 10 parts Sorbitose C-5 (etherified starch-based sizing agent) 5 parts Snow Algin 5SL (sodium alginate-based sizing agent) 55
Part: Water: 30 parts: Total: 100 parts The alkaline discharge printing paste having the above composition is printed on a processed polyester yarn fabric, and is dried intermediately. Next, a printing dyeing paste having the following composition is overprinted.

Dye composition from the monoazo compound described in Example 1 6 parts Sorbitose C - 55 parts Snow Algin SSL 60 parts Water 34 parts Total 100 parts After intermediate drying, steaming at 130°C for 20 minutes, washing with water, washing with hot water, washing with refluxed water. do. A red printed pattern-dyed fabric with excellent white discoloration in the area printed with alkaline discharge printing paste is obtained.

Patent applicant: Nippon Kayaku Co., Ltd.

Claims (2)

[Claims] (1) Formula (I) [2] When X in (I) is a methoxycarbonyl group or an ethoxycarbonyl group, Y is a methoxycarbonyl group or an ethoxycarbonyl group, and X is a phenylsulfonyl group, a methylsulfonyl group, or an ethylsulfonyl group. When a group, Y represents hydrogen, a methoxycarbonyl group or an ethoxycarbonyl group, and R represents hydrogen, a methyl group or an ethyl group. 1 represents the following formula (III), (IV), and M. ■ Also in 8 (Formula (ff), (III), GV) and ■, R1 is hydrogen, chloro, methyl group, methoxy group, ethoxy group, acetylamino group, propionylamino group, benzoylamino group, methylsulfonyl-amino group or ethylsulfonylamino group, R2 is hydrogen, chloro, methyl group, methoxy group or ethoxy group, R4 is hydrogen,
Alkyl group having 1 to 4 carbon atoms, allyl group, benzyl group, cyanethyl group, alkoxyalkyl group having 3 to 4 carbon atoms,
A hydroxyalkyl group having 2 to 4 carbon atoms, an acyloxyalkylated group having 4 to 6 carbon atoms, an alkoxycarbonylalkyl group having 3 to 7 carbon atoms, or an alkoxycarbonyloxyalkyl group having 4 to 7 carbon atoms (however, both R3 and R4 (5 is chloro or methyl group,
R6 is hydrogen, a methyl group or a phenyl group, R7 is a methyl group or an alkoxycarbonyl group having 2 to 5 carbon atoms, and 8 is hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 4 to 7 carbon atoms. Represent each. )] A monoazo compound represented by (2) Formula (I) [When X in formula (I) is a methoxycarbonyl group or an ethoxycarbonyl group, Y is a methoxycarbonyl group or an ethoxycarbonyl group, and X is a phenylsulfonyl group, a methylsulfonyl group, or an ethylsulfonyl group When , Y is hydrogen,
Each represents a methoxycarbonyl group or an ethoxycarbonyl group, and R represents hydrogen, a methyl group or an ethyl group. I(represents the following formula (II), (III), Gv) or (V). 8 (However, shi type (■), (■), aV) and h (V) nioite■
R2 is hydrogen, chloro, methyl group, methoxy group, ethoxy group, acetylamino group, glopionylamino group, benzoylamino group, methylsulfonylamino group, or ethylsulfonylamino group, and R2 is hydrogen, chloro, methyl group,
Methoxy group or ethoxy group, 3.几4 is hydrogen, an alkyl group having 1 to 4 carbon atoms, an allyl group, a benzyl group, a cyanoethyl group, an alkoxyalkyl group having 3 to 4 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an acyloxy group having 4 to 6 carbon atoms Alk/L4, an alkoxycarbonylalkyl group having 3 to 7 carbon atoms or an alkoxycarbonyloxyalkyl group having 4 to 7 carbon atoms (however, YL3.几 are not both hydrogen), and lt5 is a chlor or methyl group. , 几6 is hydrogen, a methyl group or a phenyl group, t7 is a methyl group or an alkoxycarbonyl group having 2 to 5 carbon atoms, Rs is hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 4 carbon atoms
~7 alkoxyalkyl groups, respectively. )] A dyeing method for hydrophobic fibers characterized by using a monoazo compound represented by